organic compounds
2,2′-Diazinodimethylidyne)di-o-phenylene) dibenzoate
aDepartment of Solid State Physics, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India, bDepartment of Physics, Jadavpur University, Kolkata 700 032, India, cDepartment of Chemistry, Jadavpur University, Kolkata 700 032, India, and dDepartment of Chemistry, University of Manchester, Manchester M13 9PL, England
*Correspondence e-mail: sspmm@iacs.res.in
The title compound, C28H20N2O4, was synthesized by the reaction of 2-(hydrazonomethyl)phenyl benzoate with iodine. The molecule possesses a crystallographically imposed center of symmetry at the mid-point of the hydrazine N—N bond. The substituents at the ends of the C=N bonds adopt an E,E configuration. Intermolecular C—H⋯π(arene) hydrogen bonds and aromatic π–π stacking interactions [centroid–centroid distance 3.900 (1) Å] link the molecules into (100) sheets. In addition, there is an intermolecular C—H⋯O hydrogen-bond interaction.
Related literature
For related literature, see: Glaser et al. (1995); Kesslen et al. (1999); Hunig et al. (2000); Glidewell et al. (2006); Xu & Hu (2007); Zheng et al. (2006); Liu et al. (2007).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: SMART (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
Supporting information
10.1107/S1600536808010155/fj2111sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808010155/fj2111Isup2.hkl
A solution of iodine(8 g, 7 mmol) in 15 ml tetrahydrofuran (THF) was added dropwise to a magnetically stirred solution of 2- benzoyloxy phenyl hydrazone (0.68 g, 2.8 mmol) in THF (40 ml) and triethylamine (10 ml) at room temperature (298k). The mixture was stirred for 1 h and then diluted with water (100 ml) and extracted with ether (3x30 ml). The extract was washed with water, aqueous sodium thiosulfate solution and brine followed by drying over anhydrous sodium sulfate. The solvent was removed in vacuo. The residual black oil was dissolved in carbon tetrachloride and filtered through silica gel to give a light yellow oil which on standing yielded shinny yellow crystals of the title compound (I).
All H atoms were positioned geometrically and refined using a riding model with Uiso(H) values fixed at 1.2Ueq(C).
Data collection: SMART (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).C28H20N2O4 | Z = 1 |
Mr = 448.46 | F(000) = 234 |
Triclinic, P1 | Dx = 1.357 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.5442 (9) Å | Cell parameters from 1976 reflections |
b = 7.9966 (13) Å | θ = 2.4–27.5° |
c = 13.455 (2) Å | µ = 0.09 mm−1 |
α = 73.201 (2)° | T = 100 K |
β = 82.066 (3)° | Block, pale yellow |
γ = 74.441 (2)° | 0.35 × 0.20 × 0.20 mm |
V = 548.94 (15) Å3 |
Bruker SMART CCD area-detector diffractometer | 1692 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.117 |
Graphite monochromator | θmax = 25.0°, θmin = 1.6° |
ϕ and ω scans | h = −6→3 |
2797 measured reflections | k = −9→9 |
1885 independent reflections | l = −15→15 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0874P)2 + 0.0721P] where P = (Fo2 + 2Fc2)/3 |
1885 reflections | (Δ/σ)max < 0.001 |
154 parameters | Δρmax = 0.24 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C28H20N2O4 | γ = 74.441 (2)° |
Mr = 448.46 | V = 548.94 (15) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.5442 (9) Å | Mo Kα radiation |
b = 7.9966 (13) Å | µ = 0.09 mm−1 |
c = 13.455 (2) Å | T = 100 K |
α = 73.201 (2)° | 0.35 × 0.20 × 0.20 mm |
β = 82.066 (3)° |
Bruker SMART CCD area-detector diffractometer | 1692 reflections with I > 2σ(I) |
2797 measured reflections | Rint = 0.117 |
1885 independent reflections |
R[F2 > 2σ(F2)] = 0.051 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.24 e Å−3 |
1885 reflections | Δρmin = −0.28 e Å−3 |
154 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | −0.60203 (19) | −0.17401 (13) | 0.23034 (8) | 0.0250 (3) | |
O2 | −0.3270 (2) | −0.15072 (14) | 0.33163 (8) | 0.0299 (3) | |
N1 | −0.1081 (2) | 0.06358 (16) | 0.01102 (9) | 0.0256 (3) | |
C1 | −0.2578 (3) | −0.01150 (19) | 0.07886 (11) | 0.0246 (4) | |
H1 | −0.2140 | −0.1383 | 0.1073 | 0.029* | |
C2 | −0.4964 (3) | 0.09474 (19) | 0.11375 (11) | 0.0239 (4) | |
C3 | −0.5716 (3) | 0.2813 (2) | 0.07164 (12) | 0.0273 (4) | |
H3 | −0.4643 | 0.3410 | 0.0206 | 0.033* | |
C4 | −0.7999 (3) | 0.3799 (2) | 0.10330 (12) | 0.0291 (4) | |
H4 | −0.8471 | 0.5066 | 0.0747 | 0.035* | |
C5 | −0.9593 (3) | 0.2945 (2) | 0.17645 (12) | 0.0287 (4) | |
H5 | −1.1170 | 0.3624 | 0.1972 | 0.034* | |
C6 | −0.8898 (3) | 0.1100 (2) | 0.21961 (11) | 0.0263 (4) | |
H6 | −0.9986 | 0.0508 | 0.2700 | 0.032* | |
C7 | −0.6600 (3) | 0.01385 (19) | 0.18816 (11) | 0.0240 (4) | |
C8 | −0.4341 (3) | −0.24172 (19) | 0.30508 (11) | 0.0228 (4) | |
C9 | −0.3993 (3) | −0.43981 (19) | 0.34806 (11) | 0.0231 (4) | |
C10 | −0.2123 (3) | −0.5285 (2) | 0.41615 (12) | 0.0264 (4) | |
H10 | −0.1100 | −0.4633 | 0.4326 | 0.032* | |
C11 | −0.1736 (3) | −0.7120 (2) | 0.46053 (12) | 0.0283 (4) | |
H11 | −0.0454 | −0.7729 | 0.5076 | 0.034* | |
C12 | −0.3236 (3) | −0.8067 (2) | 0.43577 (12) | 0.0293 (4) | |
H12 | −0.2985 | −0.9326 | 0.4664 | 0.035* | |
C13 | −0.5087 (3) | −0.7186 (2) | 0.36691 (12) | 0.0287 (4) | |
H13 | −0.6087 | −0.7845 | 0.3496 | 0.034* | |
C14 | −0.5495 (3) | −0.5342 (2) | 0.32285 (12) | 0.0264 (4) | |
H14 | −0.6781 | −0.4733 | 0.2761 | 0.032* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0317 (6) | 0.0174 (6) | 0.0274 (6) | −0.0070 (4) | −0.0069 (4) | −0.0048 (4) |
O2 | 0.0394 (6) | 0.0212 (6) | 0.0337 (6) | −0.0127 (5) | −0.0095 (5) | −0.0061 (4) |
N1 | 0.0305 (7) | 0.0198 (6) | 0.0267 (7) | −0.0039 (5) | −0.0036 (5) | −0.0077 (5) |
C1 | 0.0334 (8) | 0.0167 (7) | 0.0249 (7) | −0.0057 (6) | −0.0065 (6) | −0.0058 (6) |
C2 | 0.0307 (8) | 0.0199 (8) | 0.0233 (7) | −0.0067 (6) | −0.0049 (6) | −0.0073 (6) |
C3 | 0.0328 (8) | 0.0211 (8) | 0.0280 (8) | −0.0075 (6) | −0.0037 (6) | −0.0049 (6) |
C4 | 0.0362 (9) | 0.0177 (7) | 0.0329 (8) | −0.0037 (6) | −0.0076 (6) | −0.0061 (6) |
C5 | 0.0290 (8) | 0.0261 (8) | 0.0326 (8) | −0.0023 (6) | −0.0052 (6) | −0.0129 (6) |
C6 | 0.0294 (8) | 0.0265 (8) | 0.0264 (8) | −0.0095 (6) | −0.0026 (6) | −0.0093 (6) |
C7 | 0.0317 (8) | 0.0176 (7) | 0.0257 (8) | −0.0062 (6) | −0.0089 (6) | −0.0068 (6) |
C8 | 0.0270 (7) | 0.0201 (8) | 0.0224 (7) | −0.0067 (6) | −0.0005 (6) | −0.0070 (6) |
C9 | 0.0274 (8) | 0.0201 (8) | 0.0240 (7) | −0.0077 (6) | 0.0005 (6) | −0.0083 (6) |
C10 | 0.0311 (8) | 0.0226 (8) | 0.0285 (8) | −0.0090 (6) | −0.0039 (6) | −0.0083 (6) |
C11 | 0.0316 (8) | 0.0223 (8) | 0.0293 (8) | −0.0043 (6) | −0.0047 (6) | −0.0050 (6) |
C12 | 0.0360 (9) | 0.0169 (7) | 0.0337 (8) | −0.0064 (6) | 0.0019 (6) | −0.0065 (6) |
C13 | 0.0318 (8) | 0.0222 (8) | 0.0366 (9) | −0.0108 (6) | −0.0003 (6) | −0.0114 (6) |
C14 | 0.0283 (8) | 0.0214 (8) | 0.0310 (8) | −0.0069 (6) | −0.0028 (6) | −0.0081 (6) |
O1—C8 | 1.3580 (18) | C6—C7 | 1.381 (2) |
O1—C7 | 1.4073 (17) | C6—H6 | 0.9500 |
O2—C8 | 1.2045 (17) | C8—C9 | 1.489 (2) |
N1—C1 | 1.274 (2) | C9—C10 | 1.382 (2) |
N1—N1i | 1.408 (2) | C9—C14 | 1.393 (2) |
C1—C2 | 1.466 (2) | C10—C11 | 1.384 (2) |
C1—H1 | 0.9500 | C10—H10 | 0.9500 |
C2—C7 | 1.390 (2) | C11—C12 | 1.392 (2) |
C2—C3 | 1.401 (2) | C11—H11 | 0.9500 |
C3—C4 | 1.384 (2) | C12—C13 | 1.380 (2) |
C3—H3 | 0.9500 | C12—H12 | 0.9500 |
C4—C5 | 1.383 (2) | C13—C14 | 1.389 (2) |
C4—H4 | 0.9500 | C13—H13 | 0.9500 |
C5—C6 | 1.387 (2) | C14—H14 | 0.9500 |
C5—H5 | 0.9500 | ||
C8—O1—C7 | 116.52 (10) | C2—C7—O1 | 120.43 (13) |
C1—N1—N1i | 111.37 (15) | O2—C8—O1 | 123.28 (13) |
N1—C1—C2 | 121.02 (13) | O2—C8—C9 | 125.08 (13) |
N1—C1—H1 | 119.5 | O1—C8—C9 | 111.63 (12) |
C2—C1—H1 | 119.5 | C10—C9—C14 | 120.38 (14) |
C7—C2—C3 | 117.32 (14) | C10—C9—C8 | 117.36 (13) |
C7—C2—C1 | 121.33 (13) | C14—C9—C8 | 122.25 (13) |
C3—C2—C1 | 121.33 (13) | C9—C10—C11 | 120.26 (13) |
C4—C3—C2 | 120.94 (14) | C9—C10—H10 | 119.9 |
C4—C3—H3 | 119.5 | C11—C10—H10 | 119.9 |
C2—C3—H3 | 119.5 | C10—C11—C12 | 119.53 (14) |
C5—C4—C3 | 120.14 (14) | C10—C11—H11 | 120.2 |
C5—C4—H4 | 119.9 | C12—C11—H11 | 120.2 |
C3—C4—H4 | 119.9 | C13—C12—C11 | 120.28 (14) |
C4—C5—C6 | 120.20 (14) | C13—C12—H12 | 119.9 |
C4—C5—H5 | 119.9 | C11—C12—H12 | 119.9 |
C6—C5—H5 | 119.9 | C12—C13—C14 | 120.35 (13) |
C7—C6—C5 | 118.95 (14) | C12—C13—H13 | 119.8 |
C7—C6—H6 | 120.5 | C14—C13—H13 | 119.8 |
C5—C6—H6 | 120.5 | C13—C14—C9 | 119.19 (14) |
C6—C7—C2 | 122.43 (14) | C13—C14—H14 | 120.4 |
C6—C7—O1 | 117.04 (13) | C9—C14—H14 | 120.4 |
N1i—N1—C1—C2 | −179.77 (13) | C8—O1—C7—C2 | 78.69 (16) |
N1—C1—C2—C7 | −179.63 (13) | C7—O1—C8—O2 | −3.9 (2) |
N1—C1—C2—C3 | 1.9 (2) | C7—O1—C8—C9 | 176.64 (11) |
C7—C2—C3—C4 | 0.0 (2) | O2—C8—C9—C10 | −6.7 (2) |
C1—C2—C3—C4 | 178.48 (13) | O1—C8—C9—C10 | 172.76 (12) |
C2—C3—C4—C5 | −0.9 (2) | O2—C8—C9—C14 | 172.44 (14) |
C3—C4—C5—C6 | 1.0 (2) | O1—C8—C9—C14 | −8.13 (19) |
C4—C5—C6—C7 | −0.1 (2) | C14—C9—C10—C11 | −0.4 (2) |
C5—C6—C7—C2 | −0.8 (2) | C8—C9—C10—C11 | 178.68 (12) |
C5—C6—C7—O1 | −177.14 (12) | C9—C10—C11—C12 | 0.3 (2) |
C3—C2—C7—C6 | 0.9 (2) | C10—C11—C12—C13 | 0.4 (2) |
C1—C2—C7—C6 | −177.63 (13) | C11—C12—C13—C14 | −1.0 (2) |
C3—C2—C7—O1 | 177.10 (12) | C12—C13—C14—C9 | 0.8 (2) |
C1—C2—C7—O1 | −1.4 (2) | C10—C9—C14—C13 | −0.1 (2) |
C8—O1—C7—C6 | −104.90 (14) | C8—C9—C14—C13 | −179.14 (12) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O2ii | 0.95 | 2.64 | 3.519 (2) | 154 |
C5—H5···Cg1iii | 0.95 | 2.79 | 3.510 (2) | 133 |
Symmetry codes: (ii) x−1, y, z; (iii) x−1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C28H20N2O4 |
Mr | 448.46 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 5.5442 (9), 7.9966 (13), 13.455 (2) |
α, β, γ (°) | 73.201 (2), 82.066 (3), 74.441 (2) |
V (Å3) | 548.94 (15) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2797, 1885, 1692 |
Rint | 0.117 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.135, 1.03 |
No. of reflections | 1885 |
No. of parameters | 154 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.24, −0.28 |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O2i | 0.95 | 2.64 | 3.519 (2) | 153.5 |
C5—H5···Cg1ii | 0.95 | 2.79 | 3.510 (2) | 133 |
Symmetry codes: (i) x−1, y, z; (ii) x−1, y+1, z. |
Acknowledgements
The authors thank Prof. A. K. Mukherjee of the Department of Physics, Jadavpur University, for his interest and for stimulating discussions.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The synthetic utility of hydrazine compounds in coordination chemistry as well as their remarkable photochromic properties has resulted in continued interest in studies of their stereochemistry (Glaser et al., 1995). The photochromism in hydrazines arises from intramolecular H-atom transfer, together with a change in the π-electron system. To study the effect of intermolecular interactions, such as π···π charge transfer or hydrogen bonding, on H-atom transfer processes, solid state structure analyses of a number of hydrazine compounds containing both a diamine linkage and N—N bonding have been reported in the literature (Liu et al., 2007; Xu & Hu, 2007; Zheng et al., 2006) We report here the synthesis and molecular structure of the title benzylidenehydrazine derivative(I).
As observed in many symmetric azines with an E, E configuration (Glidewell et al., 2006), the molecule of (I) possesses a crystallographically imposed center of symmetry at the mid-point of the N—N bond (Fig. 1). Consequently the asymmetric unit consists of half of the molecule. The central –CH=N—N=CH– fragment is strictly planar, but as a whole the molecule is not planar; the benzoyloxy group (C8—C14, O1, O2) is rotated about the O1—C7 bond by 78.7 (2)° with respect to the plane of the benzylidene hydrazine moiety (C1—C7, N1). The single-bond character of N1—N1i[1.408 (2) Å] and the double-bond character of C1=N1[1.274 (2) Å] indicate a lack of delocalization of π-electrons, while the planar structure of >C=N—N=C< chain indicates π configuration. The C=N—N angle [11.4 (2)°] in (I) is significantly smaller than the ideal sp2value of 120°, as consequence of repulsion between the nitrogen lone pairs and the adjacent C=N bond.
The supramolecular aggregation in (I) is determined by C—H···π (arene) hydrogen bond and aromatic π···π stacking interactions. The aryl C5 atom in the ring at (x, y, z) is part of the molecule centered across (0, 0, 0) and acts as a hydrogen bond donor to the aryl ring (C9—C14) at (-1 + x, 1 + y, z), which forms part of the molecule centered across (-1, 1, 0). Propagation of this hydrogen-bond forms a chain running parallel to the [11 0] direction (Fig. 2). The phenyl rings (C9—C14) at (x, y, z) and (1 - x, 1 - y,1 - z) are components of the molecules across the inversion centers at (0, 0, 0) and (1 - x, 1 - y, 1 - z), respectively. These strictly parallel rings with an interplanar spacing of 3.464 (1) Å, the ring-centroid separation of 3.900 (1)Å and the centroid offset of 1.79Å lead to the formation of a π-stacked chain of centrosymmetric molecules running parallel to the [1 1 1] direction (Fig. 2).The combination of the [110] and [1 1 1] chains generates a (100) sheet.